Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
  • A61K8/466—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfonic acid derivatives; Salts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
  • C07C311/12—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
  • C07C311/13—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings the carbon skeleton containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
  • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
  • C07C311/19—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom to an acyclic carbon atom of a hydrocarbon radical substituted by carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
  • C07D317/54—Radicals substituted by oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
  • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/05—Stick

Definitions

• the present invention relates to new sulphonamides derived from 3-benzylidenecamphor and their use in the field of cosmetics, particularly as sunscreens.
• UV-B rays of wavelengths between 280 and 320 nm play a predominant part in the production of solar erythema and must therefore be filtered out
• UV-A rays of wavelengths between 320 and 400 nm which make the skin tan, are also capable of inducing a change in the latter, especially in the case of a sensitive skin or of a skin which is continually exposed to solar radiation.
• UV-A rays cause a loss of skin elasticity and the appearance of wrinkles, leading to premature aging. They promote the triggering of the erythemateous reaction or intensify this reaction in some individuals and may even be at the source of phototoxic or photoallergic reactions.
• the applicants have found new sulphonamides derived from amino acids and from benzylidenecamphor exhibiting good chemical and photochemical stability in addition to good screening power in the wavelength range from 280 to 380 nm. These compounds also exhibit the advantage of not being toxic or irritant and of being perfectly harmless to the skin. Furthermore, the compounds according to the invention endow the cosmetic compositions and especially those for protection against sunlight in which they are employed with good adhesion to skin, and this avoids repeated applications during the exposure to sunlight.
• the compounds according to the invention which are water-soluble or lipid-soluble, exhibit good solubility in the usual cosmetic solvents.
• the subject-matter of the present invention is therefore new sulphonamides derived from 3-benzylidenecamphor of general formula: ##STR1## in which
• X 1 denotes a hydrogen atom or the radical Y
• X 2 denotes a hydrogen or halogen atom, a C 1 -C 4 alkyl or alkoxy radical or a radical Y or Z,
• X 3 denotes a hydrogen or halogen atom, a C 1 -C 4 alkyl or alkoxy radical or a radical Y or Z,
• X 2 and X 3 together form an alkylenedioxy group in which the alkylene group contains 1 or 2 carbon atoms,
• Y denotes a group ##STR2## denotes an optionally esterified amino acid residue in which:
• R 1 and R 2 denote a hydrogen atom, an alkyl or hydroxyalkyl group, at least one of these two radicals denoting a group of formula:
• R 3 may also form with R 1 or R 2 and the nitrogen atom to which they are attached, a heterocyclic ring such as, for example, a proline or hydroxyproline residue,
• R 4 denotes a hydrogen atom or an alkyl, aralkyl or aryl group, or
• n and R 4 having the same values as above and R 6 denoting a hydrogen atom or an alkyl, aralkyl or aryl group, or
• X 1 denotes a hydrogen atom and X 3 has the value Y
• X 2 is preferably other than a hydrogen atom.
• the process for the preparation of the compounds of formula (I) according to the invention is a two-step process employing, as starting material, the sulphonic acid corresponding to the required sulphonamides, or its alkali metal salt.
• the first step consists in preparing the sulphonyl chloride by reacting the starting sulphonic acid or its alkali metal salt with phosphorus pentachloride or with thionyl chloride, optionally in the presence of an inert solvent such as the chlorinated solvents in the conditions described in French Patent 2,529,887.
• the starting sulphonic acid may be prepared as indicated in French Patents 2,282,426, 2,237,882 and 2,430,938.
• an amino acid or an ester of an amino acid is reacted with sulphonyl chloride in the presence of an inorganic or organic base to trap the hydrochloric acid which forms, optionally in the presence of an inert solvent such a chlorinated solvents.
• a hydrolysis of this ester group may be carried out after the condensation reaction with sulphonyl chloride.
• This hydrolysis may be carried out by means of an alkaline or alkaline-earth base in a solvent such as water or alcohols at a temperature close to the boiling point of the solvent.
• amino acids there may be mentioned: glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, tryptophan, histidine, ornithine, lysine, serine, threonine, cysteine, methionine, aspartic and glutamic acids, asparagine, glutamine, proline, hydroxyproline and cystine.
• the preferred amino acids are phenylalanine, tyrosine, glycine, glutamic acid, alanine, cystine and their methyl, ethyl, butyl and tetradecyl esters.
• the compounds obtained with an amino acid ester are lipid-soluble, whereas the compounds obtained with an amino acid are water-soluble after the acid functional group is converted into salt with an alkali metal or ammonium hydroxide or an amine such as triethanolamine, diisopropanolamine or 2-amino-2-methyl-1-propanol.
• Another subject of the invention is the use in cosmetics of the sulphonamides derived from amino acids and from benzylidenecamphor having the formula (I), especially as agents filtering out the UV rays of wavelengths ranging from 280 to 380 nm.
• compositions containing an effective quantity of at least one compound of formula (I) in a cosmetically acceptable medium and capable of being employed as compositions protecting human skin or hair or as compositions for protection against sunlight.
• Another subject of the invention consists of a cosmetic composition, colored or otherwise, stabilized against light, comprising an effective quantity of at least one benzylidenecamphor derivative of the formula (I).
• compositions according to the invention When employed as compositions intended to protect human skin against ultraviolet rays, they may be in the most diverse forms usually employed in the case of a composition of this type and particularly in the form of oily or alcoholic oil lotions, of emulsions such as a cream or a milk, of alcoholic oil, alcoholic or hydroalcoholic gels, or are packaged as an aerosol or as solid sticks.
• compositions of this type may contain the cosmetic adjuvants usually employed in a composition of this type, such as thickeners, softeners, humectants, surfactants, preservatives, antifoams, perfumes, oils, waxes, lanolin, propellants, colorants and/or pigments, the purpose of which is to color the composition itself or the skin, or any other ingredient usually employed in cosmetics.
• cosmetic adjuvants usually employed in a composition of this type, such as thickeners, softeners, humectants, surfactants, preservatives, antifoams, perfumes, oils, waxes, lanolin, propellants, colorants and/or pigments, the purpose of which is to color the composition itself or the skin, or any other ingredient usually employed in cosmetics.
• the compound of formula (I) is present particularly in proportions by weight of between 0.25 and 3% relative to the total weight of the composition.
• the solvent used for solubilizing may be an oil, a wax and, in general, any fatty substance, a monoalcohol, a lower polyol or mixtures thereof.
• Monoalcohols or polyols which are particularly preferred are ethanol, isopropanol, propylene glycol, glycerine or sorbitol.
• An embodiment of the invention is an emulsion in the form of protective cream or milk containing, in addition to the compound of formula (I), fatty alcohols, fatty acid esters such as triglycerides of fatty acids, fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers, in the presence of water.
• fatty alcohols such as triglycerides of fatty acids, fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers
• Another embodiment consists of oily lotions based on natural or synthetic oils and waxes, of lanolin and of fatty acid esters such as triglycerides of fatty acids and of alcoholic oil lotions based on lower alcohols such as ethanol, or of glycols such as propylene glycol and/or polyols such as glycerine and oils, waxes and fatty acid esters such as the triglycerides of fatty acids.
• the cosmetic composition of the invention may also be an alcoholic or hydroalcoholic gel comprising one or more lower alcohols or polyols such as ethanol, propylene glycol or glycerine and a thickener.
• the alcoholic oil gels additionally contain an oil or a natural or synthetic wax.
• the solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acid esters, lanolin and other fatty substances.
• compositions according to the invention When the compositions according to the invention are employed as cosmetic compositions for protection against sunlight, they contain at least one compound of formula (I), which may be used in combination, if desired, with another sunscreen specific for the UV-B radiation or the UV-A radiation and compatible with the compounds of formula (I).
• Two filters according to the invention one filtering in the UV-B and the other in the UV-A, may be advantageously employed in the compositions for protection against sunlight. A formulation filtering out both UV-B and UV-A rays is thus obtained.
• the total quantity of filters in the compositions for protection against sunlight namely the compound(s) of formula (I) and the other filters if appropriate, is between 0.5 and 15% by weight relative to the total weight of the composition.
• These compositions for protection against sunlight are in the forms indicated above in the case of the compositions which protect human skin.
• sunscreens filtering out the UV-B rays there may be mentioned water-soluble filters such as the benzylidenecamphor derivatives described in the Applicant's French Patents 2,199,971, 2,236,515, 2,282,426 and 2,383,904 and more particularly 4-(2-oxo-3-bornylidenemethyl)phenyltrimethylammonium methyl sulphate, and salts of 4-(2-oxo-3-bornylidenemethyl)benzenesulphonic acid, of 2-methyl-5-(2-oxo-3-bornylidene)benzenesulphonic acid and of 2-phenylbenzimidazole-5-sulphonic acid.
• water-soluble filters such as the benzylidenecamphor derivatives described in the Applicant's French Patents 2,199,971, 2,236,515, 2,282,426 and 2,383,904 and more particularly 4-(2-oxo-3-bornylidenemethyl)phenyltrimethylammonium methyl sulphate, and salt
• UV-B filters consisting of lipid-soluble compounds or of oils having screening properties such as, in particular, coffee oil.
• UV-B sunscreens there maY be mentioned esters of salicylic acid such as 2-ethylhexyl salicylate, homomenthyl salicylate, esters of cinnamic acid such as 2-ethylhexyl p-methoxycinnamate or 2-ethoxyethyl p-methoxycinnamate, esters of p-aminobenzoic acid such as amyl p-aminobenzoate or 2-ethylhexyl p-dimethylaminobenzoate, benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone or 2,2'-dihydroxy-4-methoxybenzophenone, camphor derivatives such as 3-(4'-methylbenzylidene)camphor or 3-benzylidenecamphor,
• the compounds according to the invention may also be used in combination with UV-A filters among which there may be mentioned dibenzoylmethane derivatives such as those described in French Patent Application 2,440,933 and German Patent Application 2,544,180.
• the present invention is also aimed at a process for protecting cosmetic compositions colored or otherwise, consisting in incorporating in these compositions an effective quantity of at least one compound of formula (I) as an agent for protection against ultraviolet rays.
• compositions may consist of hair-care compositions such as hair lacquers, hair setting lotions which may be conditioning or disentangling if desired, shampoos, coloring shampoos, make-up products such as nail varnishes, skin treatment creams, foundations, lipsticks, and any other cosmetic composition capable, because of its constituents, of presenting problems of stability to light during storage.
• hair-care compositions such as hair lacquers, hair setting lotions which may be conditioning or disentangling if desired
• shampoos coloring shampoos
• make-up products such as nail varnishes, skin treatment creams, foundations, lipsticks, and any other cosmetic composition capable, because of its constituents, of presenting problems of stability to light during storage.
• Such compositions contain 0.1 to 3% by weight of the compound of formula (I).
• a further subject-matter of the present invention is a process for protecting the skin against UV radiation consisting in applying to the skin an effective quantity of at least one compound of formula (I) present in a cosmetically acceptable carrier.
• the compound of Example 3 is prepared in the following manner:
• the reaction mixture is refluxed for 2 hours.
• the triethylamine salt is filtered off.
• the filtrate is washed with water, is dried over sodium sulphate and is then concentrated under vacuum.
• the compounds (I) according to the invention may be introduced into the following cosmetic compositions:
• the filters are dissolved in the fatty phase, which is heated to about 75°-80° C.
• the aqueous phase containing the glycerine and the emulsifier is heated to about 75-80° C. with vigorous stirring; the fatty phase is added to the aqueous phase and cooling is allowed to take place with moderate stirring.
• the perfume and the preservative are added at about 40° C.
• the filter is dissolved in the fatty phase containing the emulsifier, which is heated to about 75°-80° C.
• the aqueous phase containing the propylene glycol is heated to about 75°-80° C. and the aqueous phase is added to the fatty phase with vigorous stirring. Cooling is allowed to take place with moderate stirring and the perfume and the preservative are added to about 40° C.

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• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Veterinary Medicine (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Dermatology (AREA)
• Cosmetics (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=19731002

Family Applications (1)

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Cited By (10)

Families Citing this family (1)

Citations (7)

• 1987
  • 1987-12-22 LU LU87089A patent/LU87089A1/fr unknown
• 1988
  • 1988-12-16 IT IT8868117A patent/IT1234230B/it active
  • 1988-12-20 CH CH4704/88A patent/CH677111A5/fr not_active IP Right Cessation
  • 1988-12-21 JP JP63320807A patent/JPH02267A/ja active Pending
  • 1988-12-21 NL NL8803128A patent/NL8803128A/nl not_active Application Discontinuation
  • 1988-12-21 US US07/287,054 patent/US5004594A/en not_active Expired - Fee Related
  • 1988-12-21 DE DE3843107A patent/DE3843107A1/de not_active Withdrawn
  • 1988-12-21 FR FR888816930A patent/FR2624854B1/fr not_active Expired - Lifetime
  • 1988-12-21 GB GB8829811A patent/GB2211844B/en not_active Expired - Lifetime
  • 1988-12-22 BE BE8801426A patent/BE1002200A4/fr not_active IP Right Cessation

Patent Citations (7)

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